Stable concentrated fluid formulations of metal-free dyes, process for their preparation, and their use

Abstract

Concentrated fluid formulations of textile dyes, leather dyes or paper dyes, comprising (1) metal-free dyes, (2) non-ionic compounds having a hydrotropic action, at least one of components (3) or (4), component (3) being a reaction product of a fatty acid having 8 to 22 carbon atoms and 1 to 2 mols of diethanolamine, and component (4) being a compound of the formula ##STR1## in which R is an aliphatic hydrocarbon radical having 8 to 22 carbon atoms or a cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 10 to 22 carbon atoms, R 1 is hydrogen or methyl, A is --O-- or ##STR2## X is the acid radical of an inorganic, oxygen-containing acid, the acid radical of a polybasic carboxylic acid or a carboxyalkyl radical and m is a number from 1 to 50, (5) water, a water-soluble organic solvent having a boiling point of at least 80° C., or a mixture of the two, and, (6) optionally conventional formulating assistants, have excellent stability over a wide temperature range and, on dilution with water or solvents, do not form any undesired multi-phase systems or precipitates.

What is claimed is: 
     
       1. A method of preparation of a spray solution for dyeing leather, which comprises diluting a stable concentrated fluid formation with water, organic solvents, or a mixture of water and organic solvents, the fluid formulation containing, in the absence of metallized dyes: (1) a metal-free leather dye consisting essentially of a monoazo or polyazo dye or an anthraquinone dye,   (2) a non-ionic compound having a hydrotropic action, at least one of the components (3) or (4), the component   (3) being a reaction product of a fatty acid having 8 to 22 carbon atoms and 1 to 2 mols of diethanolamine, and the component   (4) being a compound of the formula ##STR13##  in which R is an aliphatic hydrocarbon radical having 8 to 22 carbon atoms or a cycloaliphatic, aromatic or aliphatic-aromatic hydrocarbon radical having 10 to 22 carbon atoms, R 1  is hydrogen or methyl, A is --O-- or ##STR14##  X is the acid radical of an inorganic oxygen containing acid, the acid radical of a polybasic carboxylic acid or a carboxyalkyl radical and m is a number from 1 to 50, and   (5) water, a water-soluble organic solvent having a boiling point of at least 80° C., or a mixture of the two.   
     
     
       2. A method according to claim 1, which contains, as the formulation component (5), a water-soluble organic solvent having a boiling point of at least 80° C., or a mixture of water and this solvent. 
     
     
       3. A method according to claim 1, which contains, in the formulation, at least 10 percent by weight of the dye, relative to the weight of the formulation. 
     
     
       4. A method according to claim 3, wherein the formulation contains 10 to 60 percent by weight of component (1), 1 to 25 percent by weight of component (2), 1 to 20 percent by weight of at least one of components (3) and (4) and 20 to 88 percent by weight of component (5), the weight percentages relating to the total formulation an the sum of the constituents adding up to 100%. 
     
     
       5. A method according to claim 4, wherein the formulation contains 10 to 30 percent by weight of component (1) 1 to 20 percent by weight of component (2), 1 to 15 percent by weight of at least one of components (3) and (4) and 20 to 88 percent by weight of component (5), the weight percentages relating to the total formulation and the sum of the constituents adding up to 100%. 
     
     
       6. A method according to claim 5, wherein the formulation contains 10 to 30 percent by weight of component (1), 3 to 20 percent by weight of component (2), 3 to 20 percent by weight of at least one of components (3) and (4) and 30 to 84 percent by weight of component (5), the weight percentages relating to the total formulation and the sum of the constituents adding up to 100%. 
     
     
       7. A method according to claim 3, wherein the formulation contains 10 to 35 percent by weight of component (1), 1 to 40 percent by weight of component (2), 1 to 40 percent by weight of at least one of components (3) and (4) and at least 5 percent by weight of water, the weight percentages relating to the total formulation and the sum of the constituents adding up to 100%. 
     
     
       8. A method according to claim 1, wherein, in the formulation, the non-ionic compound, having a hydrotropic action, representing component (2) is a reaction product, having a molecular weight of about 2,000 to 7,000, of (a 1 ) a monohydric to hexahydric alcohol having 1 to 6 carbon atoms, monalkylamines or monoalkylolmonoamines or polyalkylenepolyamines and   (a 2 ) 1,2-propylene oxide, a reaction product of an alkylene oxide and a water-insoluble aliphatic monoalcohol having at least 8 carbon atoms, a reaction product of an alkylene oxide and an arylphenol or alkylphenol, a reaction product of a saturated dicarboxylic acid having 3 to 10 carbon atoms and 1,2-propylene oxide or a polypropylene glycol, a reaction product of a fatty acid having 10 to 18 carbon atoms and 1,2-propylene oxide or a polypropylene glycol, a reaction product of a fatty acid having 10 to 18 carbon atoms, a trihydric to hexahydric alcohol and 1,2-propylene oxide or a reaction product of a fatty acid having 10 to 18 carbon atoms, a polyalkylenepolyamine and 1,2-propylene oxide.   
     
     
       9. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol or trimethylolethane and 1,2-propylene oxide. 
     
     
       10. A method according to claim 9, wherein, in the formulation, component (2) is a reaction product of a monoalkylamine or monoalkylolmonoamine having 1 to 6 carbon atoms or a polyalkylenepolyamine of the formula   H.sub.2 N(CH.sub.2 CH.sub.2 NH).sub.r CH.sub.2 CH.sub.2 NH.sub.2     in which r is 0 or a number from 1 to 3, and 1,2-propylene oxide.   
     
     
       11. A method according to claim 10, wherein, in the formulation, component (2) is a reaction product of monoisopropanolamine or ethylene diamine and 1,2-propylene oxide. 
     
     
       12. A method according to claim 8, wherein, in the formulation, component (2) is an aliphatic, saturated or unsaturated, branched or straight-chain monoalcohol having 8 to 18 carbon atoms, or a mixture of such alcohols. 
     
     
       13. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of ethylene oxide, 1,2-propylene oxide or a mixed ethylene-1,2-propylene oxide and an aliphatic, saturated or unsaturated, branched or straight-chain monoalcohol having 8 to 18 carbon atoms. 
     
     
       14. A method according to claim 13, wherein, in the formulation, component (2) is a compound of the formula   R.sub.3 O(CH.sub.2 CH.sub.2 O).sub.s H     in which R 3  is a saturated or unsaturated hydrocarbon radical having 8 to 18 carbon atoms and s is a number from 1 to 10.   
     
     
       15. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of ethylene oxide, 1,2-propylene oxide or a mixed ethylene-1,2-propylene oxide and an alkylphenol having 4 to 12 carbon atoms in the alkyl part. 
     
     
       16. A method according to claim 15, wherein, in the formulation, component (2) is a compound of the formula ##STR15## in which R 1  is hydrogen or methyl, p is a number from 4 to 12 and t is a number from 1 to 60, in particular from 1 to 30. 
     
     
       17. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of o-phenylphenol and 5 to 15 mols of ethylene oxide. 
     
     
       18. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of a saturated dicarboxylic acid having 3 to 10 carbon atoms and 1,2-propylene oxide or a polypropylene glycol. 
     
     
       19. A method according to claim 18, wherein, in the formulation, component (2) is a reaction product of adipic acid or sebacic acid and 1,2-propylene oxide or a polypropylene glycol. 
     
     
       20. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of a fatty acid having 10 to 18 carbon atoms and 1,2-propylene oxide. 
     
     
       21. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of a fatty acid having 10 to 18 carbon atoms, a trihydric to hexahydric alcohol having 3 to 6 carbon atoms and 1,2-propylene oxide. 
     
     
       22. A method according to claim 8, wherein, in the formulation, component (2) is a reaction product of a fatty acid having 10 to 18 carbon atoms, a polyalkylenepolyamine of the formula   H.sub.2 N(CH.sub.2 CH.sub.2 NH).sub.n CH.sub.2 CH.sub.2 NH.sub.2     in which n is zero or the number 1, 2 or 3, and 1,2-propylene oxide.   
     
     
       23. A method according to claim 1, wherein, in the formulation, component (3) is a reaction product of coconut fatty acid, lauric acid, oleic acid or stearic acid and 2 mols of diethanolamine. 
     
     
       24. A method according to claim 1, wherein component (4) is a compound of the formula   R--A--(CH.sub.2 CH.sub.2 O).sub.n --X     in which R, A and X are as defined in claim 1 and n is a number from 1 to 9, preferably from 1 to 4.   
     
     
       25. A method according to claim 24, wherein, in the formulation, component (4) is a compound of the formula   R.sub.2 O--(CH.sub.2 CH.sub.2 O).sub.n --X     in which R 2  is a saturated or unsaturated hydrocarbon radical, o-phenylphenyl or alkylphenyl having 4 to 12 carbon atoms in the alkyl part, and X and n are as defined in claim 24.   
     
     
       26. A method according to claim 25, wherein, in the formulation, component (4) is a compound of the formula ##STR16## in which p is a number from 4 to 12 and n and X are as defined in claim 25. 
     
     
       27. A method according to claim 26, wherein, in the formulation, component (4) is a compound of the formula ##STR17## in which q is a number from 1 to 3 and X 1  is hydrogen, NH 4  or an alkali metal cation. 
     
     
       28. A method according to claim 1, wherein component (4) is a compound of the formula ##STR18## in which R, A and X are as defined in claim 1, the sum of m 1 , m 2  and m 3  is 2 to 20 and the ratio of ethylene oxide units to propylene oxide units is 1:(1 to 2). 
     
     
       29. A method according to claim 1, wherein, in the formulation, the compounds representing component (4) are present as an alkali metal salt, ammonium salt or an amine salt. 
     
     
       30. A method according to claim 1, wherein, in the formulation, component (5) is water, a polyhydric alcohol, which is liquid at room temperature, or an ether, ester or mixed ether-ester thereof, tetramethylurea or a mixture of water and these solvents. 
     
     
       31. A method of the preparation of a stable concentrated fluid formulation of a metal-free dye, according to claim 1, which comprises mixing the dye with the components (2) and (3), (2) and (4) or (2), (3) and (4) in any desired sequence in water, a water-soluble organic solvent or mixtures thereof, optionally in the presence of conventional formulating assistants. 
     
     
       32. A method of the preparation of a stable concentrated fluid formulation of a metal-free water-soluble dye, according to claim 1, which comprises separating by-products of the synthesis, water-soluble salts and, optionally a proportion of the water from an aqueous solution or suspension of at least one metal-free water-soluble crude dye, optionally drying the resulting dye formulation, and then mixing it with the components (2) and (3), (2) and (4) or (2), (3) and (4) in any desired sequence in water, a water-soluble organic solvent or mixtures thereof, optionally in the presence of conventional formulating assistants.